Pure Appl. Chem. 2018; 90(6): 955–968 Conference paper Birgit Fischer and Volker Abetz* Determination of thermodynamic and structural quantities of polymers by scattering techniques https://doi.org/10.1515/pac-2017-1101 Abstract: Scattering techniques (i.e. light scattering, X-ray scattering, or neutron scattering) are very powerful tools to gain insights into structural and thermodynamic properties of matter which often cannot be obtained by other methods. While classical thermodynamics is independent of length scale or applies for indefinitely long length scale, scattering can disclose thermodynamic properties like the free energy or free enthalpy as functions of length scale. Scattering is caused by density or composition fluctuations, which are functions of the length scale in one- or multicomponent systems. Therefore scattering techniques can give informations about the size, shape and molecular weight of scattering objects, their thermodynamic interactions with a surrounding matrix and their dynamics if correlations of the fluctuations as function of time are investigated (i.e. dynamic light scat- tering). As scattering techniques are less intuitive in comparison to complementary techniques, i.e. microscopic techniques, the aim of this article is to highlight some relevant relationships with a focus on polymer systems. This may encourage polymer scientists to consider the use of scattering techniques to learn more about the thermodynamics of their systems and/or to gain informations about their structural properties. Keywords: POLYCHAR-25; polymers; scattering techniques; structure; thermodynamic properties. Introduction Measurements of thermodynamic properties like an osmotic pressure or the change of a boiling point of a solvent in a dilute solution can give access to the molecular weight of a dissolved (macro)molecule and its interaction with the solvent. Scattering experiments can deliver in addition structural quantities such as the size and shape of dissolved macromolecules or colloids [1–9]. In this paper we will introduce the fundamen- tal concepts of static as well as dynamic scattering experiments, which are in our opinion most relevant for characterization of polymers in solution and amorphous polymer systems. Therefore we discuss systems in which the basic structural units are on a length scale ranging from a repeating unit of a polymer up to the size of a macromolecule. We do not consider crystallographic structural investigations on the length scale of atoms. An absolute homogeneous system does not scatter, because dissolved molecules or dispersed particles are indistinguishable from their surrounding (matrix). The prerequisite for scattering is a contrast between different components or the particles of interest and the matrix. The contrast is always based on a difference (fluctuation) between the corresponding scattering properties of the particle and the matrix. The type of Article note: A collection of invited papers based on presentations at the 25th POLYCHAR 2017 World Forum on Advanced Materials Kuala Lumpur, Malaysia, October 9–13, 2017. *Corresponding author: Volker Abetz, University of Hamburg, Institute of Physical Chemistry, Grindelallee 117, 20146 Hamburg, Germany; and Helmholtz-Zentrum Geesthacht, Institute of Polymer Research, Max-Planck-Straße 1, 21502 Geesthacht, Germany, e-mail: [email protected]. http://orcid.org/0000-0002-4840-6611 Birgit Fischer: University of Hamburg, Institute of Physical Chemistry, Grindelallee 117, 20146 Hamburg, Germany © 2018 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/ 956 B. Fischer and V. Abetz: Determination of thermodynamic and structural quantities of polymers contrast depends on the probe (photons of light, X-ray photons, neutrons, electrons, α-particles …). While photons of visible light are scattered by fluctuations of the polarizability, which is related to fluctuations of the refractive index, X-ray photons are scattered by fluctuations of the electron density. Neutrons are scat- tered by the nuclei of atoms. The respective type of contrast is expressed in terms of a contrast factor which is given for these three types of probes in Table 1. The fluctuations of these quantities can be related to the fluctuation of the density δρ or the concentra- tion δc. By “fluctuation” a local deviation form a spatial average value is meant, i.e. the local concentration at space point r, c(r) deviates by the fluctuation δc(r) from the spatial average value c. Thus δc(r): = c(r) − c. Density and concentration fluctuations are related to fluctuations of the free energy dF and the free enthalpy dG, respectively. In scattering elastic and inelastic processes can occur. While in an elastic scattering event just the momentum of the probe is changed by changing its direction (i.e. Rayleigh scattering [10] or Mie scattering [11] in the case of light, or Rutherford scattering in the case of charged particles like α-particles [12]), in an inelastic scattering event (i.e. Raman scattering [13, 14] or Compton scattering [15]) also energy is transferred between scatterers and probe resulting in a change of the wavelength of the scattered probe. In Raman spec- troscopy energy of light is transferred to vibrating/rotating molecules (resulting in a so-called Stokes shift of the scattered light to longer wavelength) or internal energy is transferred from a vibrating/rotating molecule to the light (leading to a so-called Anti-Stokes shift of the scattered wavelength) [13]. While vibrational and rotational transitions lead to spectroscopically measurable shifts of the wavelength, the wavelength shifts caused by the Doppler effect of scattered light on diffusing particles is very small and the dynamic quanti- ties are obtained from the time dependence of the fluctuating scattered intensity. This is why dynamic light scattering is considered to be quasi elastic scattering, as the energy transfer between light and scatterer is extremely low. Rayleigh scattering is observed for scatterers much smaller than the wavelength of the light (point-like scatterers like gases). In case of dilute polymers in solution also Rayleigh scattering can be observed, as the macromolecules are typically not larger than ca. 1/20 of the wavelength of light. The elastic scattering of isolated spherically shaped colloidal nanoparticles with sizes in the range of the wavelength can be described by the Mie theory, which also explains the size dependence of the color [11]. However, a complete list of scattering methods would go beyond of the scope of this manuscript. For an understanding of the detailed mathematical concepts of wide angle X-ray diffraction, small angle X-ray scat- tering, and small angle light scattering we can refer to references [1, 5, 16]. In static scattering experiments, the scattered intensity arises from local inhomogeneities (local fluctua- tions) in the scattering contrast and is monitored as a function of scattering angle. The particle shape, the molar mass MW, the radius of gyration Rg and the particle interaction can be determined. In dynamic scatter- ing experiments the temporal fluctuations lead to a fluctuating scattered intensity at a fixed scattering angle Table 1: Scattering contrast factor and typical wavelength for light, neutron and X-ray experiments. Light Neutron X-rays 22 2 2 Contrast factor K π NL 222 NL 4 nS dn − rv()ρρ− ∑∑bbij2 ee,,iejm2 4 ( ij) MW MW λ0 dcm Wave length 400–700 nm 0.1–1 nm 0.1–1 nm Scattering vector 3 × 10−3–3 × 10−3 nm−1,a 5 × 10−2–5 nm−1,b 5 × 10−2–5 nm−1,b dn Here λ0 is the wavelength in vacuum, ns is the refractive index of the matrix (solvent), is the refractive index increment, dcm Σbi and Σbj are the scattering lengths of the particle i and the solvent j, MW is the weight averaged molecular weight, re is the a classical electron radius, ρe,i and ρe,j are the electron density of the particle i and the solvent j and vm is the volume. Depending on the solvent, for light scattering mostly a wavelength of about 633 nm is used. bDepending on the detector size, the detector distance and the used wavelength. B. Fischer and V. Abetz: Determination of thermodynamic and structural quantities of polymers 957 which is monitored. The diffusion coefficient can be determined from such data and in the case of dynamic light scattering of dilute polymer solutions the hydrodynamic size of the polymers can be calculated. The basic scheme of a scattering experiment is shown in Fig. 1. The incident beam passes through the sample and gets on the one hand absorbed and on the other hand scattered by the scattering objects of the sample. In a typical scattering experiment the scattering vector qk=−k is used, which is the difference fi between the wave vectors of the scattered and incident plane waves, kf and ki . The intensity of the scattered beam kf is observed at different scattering angles at a defined distance A by a detector (D). The scattering angle 2θ is the angle between transmitted and scattered beams and can usually be tuned in an experiment. While a time-averaged constant scattered intensity is monitored in static scattering at each scattering angle, a time-resolved fluctuating intensity is monitored at each scattering angle in a dynamic scattering experiment. = In elastic scattering the wave vectors have the same length (|kkfi|| |) and in quasi elastic scattering the wave vectors have almost the same length (|kkfi|| ≈ |). Therefore in both cases the scattering vector q is given by 4πn qq== || 0 sin(θ) (1) λ λ θ Here n0 is the refractive index of the scattering medium, the wavelength in vacuum and 2 is the scatter- ing angle, enclosed by kf and ki (Fig. 1). Here we will discuss the structure factor in dilute polymer solutions and in polymer bulk systems, as it can be determined from static scattering of light, X-rays, and neutrons.